CN106115659A - A kind of method of chemical gaseous phase deposition synthesizing carbon nanotubes flower - Google Patents
A kind of method of chemical gaseous phase deposition synthesizing carbon nanotubes flower Download PDFInfo
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- CN106115659A CN106115659A CN201610486841.7A CN201610486841A CN106115659A CN 106115659 A CN106115659 A CN 106115659A CN 201610486841 A CN201610486841 A CN 201610486841A CN 106115659 A CN106115659 A CN 106115659A
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- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The method that the invention discloses a kind of chemical gaseous phase deposition synthesizing carbon nanotubes flower, comprises the following steps: 1) selected base material, base material is carried out pretreatment；2) pretreated base material is placed in nickel-plating liquid carries out chemical deposition, take out, be dried, obtain the base material of supported nickel catalyst；3) base material of supported nickel catalyst is placed in tube furnace, is passed through protective atmosphere and under protective atmosphere, is warming up to 350～400 DEG C, close protective atmosphere；In tube furnace, it is passed through hydrogen and under hydrogen atmosphere, is warming up to 500～550 DEG C; then in tube furnace, it is passed through carbon-source gas, and using hydrogen as carrier gas, under the conditions of 500～550 DEG C, carries out chemical gaseous phase deposition 80～110min; gained reactant cools down under protective atmosphere, to obtain final product.The method of the invention is low for equipment requirements, and energy consumption is low, controlled to the size of Raney nickel and CNT flower.
Description
Technical field
The present invention relates to the preparation of CNT, be specifically related to the side of a kind of chemical gaseous phase deposition synthesizing carbon nanotubes flower
Method.
Background technology
CNT (CNTs) has high intensity and good toughness, electric conductivity, and specific surface area is big, and specific surface energy is high
Etc. feature.Can be used on the various fields such as large scale integrated circuit, superconducting wire, semiconductor device, Flied emission, micro-electricity.Metal Substrate
Body introduces CNTs, prepares carbon nano-tube reinforced metal-matrix composite material, be one of method obtaining high-performance metal materials.
Titanium or titanium alloy has the multiple advantages such as density is little, intensity is high, corrosion-resistant, high temperature resistant, thermal coefficient of expansion is little, especially
It is its high specific strength, is widely used in national defence and national economy field.Meanwhile, titanium material navigation, oil, chemical industry, biology,
Medicine and other fields is the most welcome.Titanium is as a kind of lightweight, corrosion resistant metal, but its mechanical performance and chemical stability are very
Difference；Although titanium alloy intensity is the highest, but wearability is bad, utilizes CNTs to improve titanium and the intensity of alloy and wearability, has very
High practical value.Liang Hao et al. utilizes ferrocene to do catalyst synthesizing carbon nanotubes (chemical vapour deposition technique system at 900 DEG C
Standby CNT, material science and technology and equipment, technology and research, the 4th phase in 2014, p4～6), but the method needs at 900 DEG C
Synthesizing carbon nanotubes, energy consumption is higher.
Summary of the invention
The technical problem to be solved in the present invention is to provide the method for a kind of chemical gaseous phase deposition synthesizing carbon nanotubes flower, the party
Method is low for equipment requirements, and energy consumption is low, controlled to the size of Raney nickel and CNT flower.
The method of chemical gaseous phase of the present invention deposition synthesizing carbon nanotubes flower, comprises the following steps:
1) selected base material, carries out pretreatment to base material；
2) pretreated base material is placed in nickel-plating liquid carries out chemical deposition, take out, be dried, obtain supported nickel catalyst
Base material；Described nickel-plating liquid is the aqueous solution of ethylene glycol, Nickel dichloride. and ammonium fluoride, consisting of: ethylene glycol 600～700ml/
L, Nickel dichloride. 10～20g/L, ammonium fluoride 10～30g/L, pH=5.0～5.5；
3) base material of supported nickel catalyst is placed in tube furnace, is passed through protective atmosphere and is warming up under protective atmosphere
350～400 DEG C, close protective atmosphere；In tube furnace, it is passed through hydrogen and under hydrogen atmosphere, is warming up to 500～550 DEG C, then
In tube furnace, it is passed through carbon-source gas, and using hydrogen as carrier gas, under the conditions of 500～550 DEG C, carries out chemical gaseous phase deposition 80
～110min, gained reactant cools down under protective atmosphere, to obtain final product.
The step 1 of said method) in, described base material can be titanium foil, Copper Foil or foam copper.Pretreatment to base material is
Pretreatment operation conventional in prior art, processes including cleaning, oil removing and etch etc..Wherein, clean typically in acetone, second
Ultrasonic cleaning in alcohol and water；During removal operation use degreasing fluid consist of: sodium hydroxide 10～15g/L, sodium carbonate 20～
30g/L, OP emulsifying agent 2～5mL/L, surplus are water；The etching solution used during etch operation forms by volume percentages and is: dense
Hydrochloric acid 20～30%, Fluohydric acid. 2～5% and the water of surplus.
The step 2 of said method) in, the time of chemical deposition may decide that Raney nickel particle size and appearance structure,
In the application, the time preferably controlling chemical deposition is 5～10min, so can make the CNT flower can be with nickle atom for urging
Agent, vertical-growth on the basis of nickel, and the carbon nanotube pitch making synthesis obtain is uniform, specific surface area is big.In this step,
It is dried and generally carries out under the conditions of 60～80 DEG C.
The step 3 of said method) in, the selection of described protective atmosphere is same as the prior art, usually argon and/or nitrogen
Gas.The speed that is passed through of protective atmosphere is usually 350～500mL/min, and the heating rate when being passed through protective atmosphere generally controls
At 5～10 DEG C/min.
The step 3 of said method) in, the selection of described carbon-source gas is same as the prior art, can be specifically methane, second
The Hydrocarbon such as alkene or acetylene.In this step, described hydrogen and carbon-source gas to be passed through speed identical, it is preferably to be 100
～200mL/min.
The step 3 of said method) in, for the protective atmosphere being passed through before replacing completely, preferably it is being passed through hydrogen
After making the temperature in tube furnace rise to 500～550 DEG C, then it is passed through hydrogen 10～20min.
Compared with prior art, present invention is characterized in that
1, the method for the invention chemical gaseous phase deposit in use first chemical plating method deposition nickel as catalyst,
Raney nickel particle size and appearance structure is controlled by the chemical deposition time, easy to operate, controlled.
2, the reaction temperature of the method for the invention is at 500～550 DEG C, hinge structure, and reaction temperature is low, and energy consumption is more
Low, equipment material is required low.
Accompanying drawing explanation
Fig. 1 is the pictorial diagram carrying out the forward and backward material of chemical gaseous phase deposition in the embodiment of the present invention 1, and wherein (a) is chemistry
The pictorial diagram of titanium foil base material before vapour deposition, (b) is the pictorial diagram of titanio CNT flower after chemical gaseous phase deposits；
Fig. 2 and Fig. 3 is the SEM figure of the titanio CNT flower that the embodiment of the present invention 1 synthesis obtains, and wherein Fig. 2 is 20000
The SEM figure of multiplying power, Fig. 3 is the SEM figure of 50000 multiplying powers；
Fig. 4 is the Raman spectrogram of the titanio CNT flower that the embodiment of the present invention 1 synthesis obtains；
Fig. 5 is the TEM figure of the titanio CNT flower that the embodiment of the present invention 1 synthesis obtains.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, to be more fully understood that present disclosure, but
The present invention is not limited to following example.
Embodiment 1
1) as base material, matrix is carried out pretreatment with titanium foil (as shown in Fig. 1 (a)), particularly as follows: respectively with acetone, ethanol
With water respectively ultrasonic cleaning 10min → electrochemical deoiling → clean water → etch → clean water → be dried；Wherein:
In electrochemical deoiling operation: consisting of of electrochemical deoiling liquid: sodium hydroxide 15g/L, sodium carbonate 25g/L, OP emulsifying agent
5mL/L and the water of surplus；Base material after ultrasonic cleaning is placed in oil removing 15min in the degreasing fluid of 60 DEG C；
In etch operation: the composition of etching solution by volume percentages is: hydrochloric acid 30%, Fluohydric acid. 5% and the water of surplus；
Base material after oil removal treatment is placed in etch 2min in etching solution, clean by clean water；
2) pretreated base material will be carried out and be placed in nickel-plating liquid chemistry chemical deposition 8min, and take out and be placed on 60 DEG C of conditions
Lower vacuum drying 10min；Described nickel-plating liquid consists of: ethylene glycol 700ml/L, Nickel dichloride. 20g/L, ammonium fluoride 15g/L and remaining
The water of amount, pH=5.0；
3) base material of supported nickel catalyst is placed in the flat-temperature zone in the middle part of tube furnace, is passed through argon with 400mL/min's
Speed is protected, and reactor is warming up to 350 DEG C with the heating rate of 10 DEG C/min, is then shut off argon；Again with 100ml/min
Flow velocity in tube furnace, be passed through hydrogen to temperature reach 500 DEG C, under conditions of tube furnace temperature reaches 500 DEG C, continue logical hydrogen
Gas (being passed through speed is 100mL/min) reductase 12 0min；Then in tube furnace, it is passed through ethylene with 150mL/min speed, 500
Chemical gaseous phase deposition 100min under the conditions of DEG C；Reactant is cooled to room temperature in argon atmosphere afterwards, obtains titanio CNT
Flower (as shown in Fig. 1 (b)).
Prepared product is characterized:
1, taking specification is that 5 × 7cm size titanio CNT flower sample SEM and TEM characterizes CNT flower surface shape
Looks structure and the uniformity of diameter and size, respectively as shown in Fig. 2, Fig. 3 and Fig. 5.
2, RAMAN characterizes crystallinity and the degree of graphitization of titanio CNT flower, as shown in Figure 4.
Embodiment 2
1) with titanium foil as base material, matrix is carried out pretreatment, particularly as follows: the most ultrasonic clearly with acetone, ethanol and water respectively
Wash 10min → electrochemical deoiling → clean water → etch → clean water → be dried；Wherein:
In electrochemical deoiling operation: consisting of of electrochemical deoiling liquid: sodium hydroxide 10g/L, sodium carbonate 30g/L, OP emulsifying agent
3mL/L and the water of surplus；Base material after ultrasonic cleaning is placed in oil removing 10min in the degreasing fluid of 50 DEG C；
In etch operation: the composition of etching solution by volume percentages is: hydrochloric acid 20%, Fluohydric acid. 3% and the water of surplus；
Base material after oil removal treatment is placed in etch 2min in etching solution, clean by clean water；
2) pretreated base material will be carried out and be placed in nickel-plating liquid chemistry chemical deposition 10min, and take out and be placed on 80 DEG C of bars
10min it is vacuum dried under part；Described nickel-plating liquid consists of: ethylene glycol 600ml/L, Nickel dichloride. 15g/L, ammonium fluoride 30g/L and
The water of surplus, pH=5.5；
3) base material of supported nickel catalyst is placed in the flat-temperature zone in the middle part of tube furnace, is passed through argon with 500mL/min's
Speed is protected, and reactor is warming up to 400 DEG C with the heating rate of 8 DEG C/min, is then shut off argon；Again with 100ml/min
Flow velocity in tube furnace, be passed through hydrogen to temperature reach 550 DEG C, under conditions of tube furnace temperature reaches 550 DEG C, continue logical hydrogen
Gas (being passed through speed is 150mL/min) reduction 10min；Then in tube furnace, it is passed through ethylene with 150mL/min speed, 550
Chemical gaseous phase deposition 80min under the conditions of DEG C；Reactant is cooled to room temperature in argon atmosphere afterwards, obtains titanio CNT
Flower.
Embodiment 3
1) with Copper Foil as base material, matrix is carried out pretreatment, particularly as follows: the most ultrasonic clearly with acetone, ethanol and water respectively
Wash 10min → electrochemical deoiling → clean water → etch → clean water → be dried；Wherein:
In electrochemical deoiling operation: consisting of of electrochemical deoiling liquid: sodium hydroxide 12g/L, sodium carbonate 20g/L, OP emulsifying agent
2mL/L and the water of surplus；Base material after ultrasonic cleaning is placed in oil removing 10min in the degreasing fluid of 50 DEG C；
In etch operation: the composition of etching solution by volume percentages is: hydrochloric acid 25%, Fluohydric acid. 2% and the water of surplus；
Base material after oil removal treatment is placed in etch 1min in etching solution, clean by clean water；
2) pretreated base material will be carried out and be placed in nickel-plating liquid chemistry chemical deposition 5min, and take out and be placed on 70 DEG C of conditions
Lower vacuum drying 150min；Described nickel-plating liquid consists of: ethylene glycol 650ml/L, Nickel dichloride. 10g/L, ammonium fluoride 20g/L and remaining
The water of amount, pH=5.25；
3) base material of supported nickel catalyst is placed in the flat-temperature zone in the middle part of tube furnace, is passed through argon with 350mL/min's
Speed is protected, and reactor is warming up to 400 DEG C with the heating rate of 8 DEG C/min, is then shut off argon；Again with 200ml/min
Flow velocity in tube furnace, be passed through hydrogen to temperature reach 520 DEG C, under conditions of tube furnace temperature reaches 520 DEG C, continue logical hydrogen
Gas (being passed through speed is 200mL/min) reduction 15min；Then in tube furnace, it is passed through ethylene with 100mL/min speed, 520
Chemical gaseous phase deposition 110min under the conditions of DEG C；Reactant is cooled to room temperature in argon atmosphere afterwards, obtains cuprio CNT
Flower.
Claims (6)
1. a method for chemical gaseous phase deposition synthesizing carbon nanotubes flower, comprises the following steps:
1) selected base material, carries out pretreatment to base material；
2) pretreated base material is placed in nickel-plating liquid carries out chemical deposition, take out, be dried, obtain the base of supported nickel catalyst
Material；Described nickel-plating liquid is the aqueous solution of ethylene glycol, Nickel dichloride. and ammonium fluoride, consisting of: ethylene glycol 600～700ml/L, chlorine
Change nickel 10～20g/L, ammonium fluoride 10～30g/L, pH=5.0～5.5；
3) base material of supported nickel catalyst is placed in tube furnace, be passed through protective atmosphere and be warming up under protective atmosphere 350～
400 DEG C, close protective atmosphere；In tube furnace, it is passed through hydrogen and under hydrogen atmosphere, is warming up to 500～550 DEG C, then to pipe
Be passed through carbon-source gas in formula stove, and using hydrogen as carrier gas, carry out under the conditions of 500～550 DEG C chemical gaseous phase deposition 80～
110min, gained reactant cools down under protective atmosphere, to obtain final product.
Method the most according to claim 1, it is characterised in that: step 1) in, described base material is titanium foil, Copper Foil or foam
Copper.
Method the most according to claim 1, it is characterised in that: step 2) in, the time of chemical deposition is 5～10min.
Method the most according to claim 1, it is characterised in that: step 3) in, described protective atmosphere is argon and/or nitrogen
Gas.
Method the most according to claim 1, it is characterised in that: step 3) in, described carbon-source gas be methane, ethylene or
Acetylene.
Method the most according to claim 1, it is characterised in that: step 3) in, described hydrogen and carbon-source gas be passed through speed
Rate is 100～200mL/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314007A (en) * | 2017-01-18 | 2018-07-24 | 中国石油化工股份有限公司 | A kind of nickel-carbon nano tube compound material and preparation method thereof |
| CN109680257A (en) * | 2019-02-19 | 2019-04-26 | 中国铝业股份有限公司 | A kind of preparation method of nano material |
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| CN1448335A (en) * | 2002-04-01 | 2003-10-15 | 财团法人工业技术研究院 | Metal catalyst for low-temp. thermochemical gas-phase precipitation synthesis of carbon nanotubes and synthetic method of carbon nanotubes using the same |
| JP2008195599A (en) * | 2007-02-15 | 2008-08-28 | Korea Inst Of Energy Research | Platinum nano catalyst-carrying carbon nano-tube electrode and its manufacturing method |
| CN104868134A (en) * | 2015-04-17 | 2015-08-26 | 华南理工大学 | Foam metal-carbon nanotube composite material, and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1448335A (en) * | 2002-04-01 | 2003-10-15 | 财团法人工业技术研究院 | Metal catalyst for low-temp. thermochemical gas-phase precipitation synthesis of carbon nanotubes and synthetic method of carbon nanotubes using the same |
| JP2008195599A (en) * | 2007-02-15 | 2008-08-28 | Korea Inst Of Energy Research | Platinum nano catalyst-carrying carbon nano-tube electrode and its manufacturing method |
| CN104868134A (en) * | 2015-04-17 | 2015-08-26 | 华南理工大学 | Foam metal-carbon nanotube composite material, and preparation method and application thereof |
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| NILAY KUMAR DEY ET AL.: "Growth of Carbon Nanotubes on Carbon Fiber by Thermal CVD Using Ni Nanoparticles as Catalysts", 《PROCEDIA ENGINEERING》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314007A (en) * | 2017-01-18 | 2018-07-24 | 中国石油化工股份有限公司 | A kind of nickel-carbon nano tube compound material and preparation method thereof |
| CN108314007B (en) * | 2017-01-18 | 2021-08-06 | 中国石油化工股份有限公司 | Nickel-carbon nanotube composite material and preparation method thereof |
| CN109680257A (en) * | 2019-02-19 | 2019-04-26 | 中国铝业股份有限公司 | A kind of preparation method of nano material |
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Effective date of registration: 20220614 Address after: 563000 Pingqiao Industrial Park, Shenxi Town, Honghuagang District, Zunyi City, Guizhou Province Patentee after: Juyuan material technology (Zunyi) Co.,Ltd. Address before: 541004 No. 15 Yucai Road, Guilin, the Guangxi Zhuang Autonomous Region Patentee before: Guangxi Normal University |